1. Field of the Invention
The present invention relates to a catalyst for olefin polymer production comprising a metallocene compound, a reaction product of topotactic reduction by electron transfer, and an organoaluminum compound, and a process for producing an olefin polymer employing the catalyst.
The present invention relates also to a catalyst for olefin polymer production comprising a metallocene compound, a product of a topotactic reduction reaction by electron transfer, an organoaluminum compound, an organoalkaline earth metal compound or an organozinc compound, and a process for producing an olefin polymer employing the catalyst.
2. Description of the Related Art
A catalyst composed of a metallocene compound and an organoaluminum compound, and another catalyst composed of a metallocene compound, an organoaluminum compound, and an organomagnesium compound are disclosed as the catalyst for producing an olefin polymer (JP-A-3-197513, and JP-A-3-290408). However, these catalysts are not satisfactory in the catalyst activity.
Active catalysts for olefin polymer production are disclosed which are composed of a metallocene compound and a methylaluminoxane (JP-A-58-19309, and JP-A-60-35007). These catalyst employs a large amount of expensive aluminoxane to produce a polymer having industrially useful properties, which causes problems of high catalyst cost and residual aluminum.
Highly active olefin polymerization catalysts not containing the methylaluminoxane are disclosed which comprises a metallocene compound, a boron compound, and an organoaluminum compound (Kohyo 1-501950, and Kohyo 1-502036). However, the boron compound for this catalyst is disadvantageously complicated and expensive.
The present invention intends to solve the above technical problems, and to provide a catalyst for olefin polymer production with high catalyst activity without using an expensive catalyst component. The present invention also provides a process for producing an olefin polymer with the catalyst.
The olefin polymerization catalyst of the present invention comprises [A] a metallocene compound containing a transition metal selected from Groups 3, 4, 5, and 6 of Periodic Table, [B] a reaction product of topotactic reduction with electron transfer, and [C] an organoaluminum compound.
The olefin polymerization catalyst of another embodiment of the present invention comprises [A] a metallocene compound containing a transition metal selected from Groups 3, 4, 5, and 6 of Periodic Table, [B] a reaction product of topotactic reduction by electron transfer, [C] an organoaluminum compound, and [D] an organoalkaline earth metal compound or an organozinc compound.
The process for producing an olefin polymer of the present invention uses the above catalyst.
The topotactic reduction with electron transfer in the present invention is a reaction, as defined by R. Schxc3x6llhorn: Angew. Chem. Int. Ed. Eng., 19, 983-1003 (1980), in which a host compound is reduced by electrons and guest are introduced into vacant lattice sites of the host compound to balance the electric charges without change of the structure and composition of the host compound by the reaction. This reaction is represented by General Formula (35) below:
xE++xexe2x88x92+xe2x96xa1[Q]xe2x86x92(E+)x[Q]xxe2x88x92xe2x80x83xe2x80x83(35)
where [Q] is the host compound, xe2x96xa1 is a vacant lattice site of [Q], exe2x88x92 is an electron, x is a number of reduction, and E+ is a monovalent guest cation.
The component [B] in the present invention is a reaction product of the above electron-transferring topotactic reduction, and is represented by General Formula (36):
En+(k/n)(L2)h[Q]kxe2x88x92xe2x80x83xe2x80x83(36)
where [Q] is a host compound, k is a number of reduction, En+ is an n-valent guest cation, L2 is a Lewis base, and h is a number of the Lewis base.
The host compound [Q] includes host compounds of three-dimensional structure, host compounds of two-dimensional structure, host compounds of one-dimensional structure, and host compounds of a molecular solid.
The host compounds of three-dimensional structure include hexamolybdenum octasulfide, hexamolybdenum octaselenide, trimolybdenum tetrasulfide, trititanium tetrasulfide, hexatitanium octaselenide, triniobium tetrasulfide, hexavanadium octasulfide, pentavanadium octasulfide, divanadium pentaoxide, tungsten trioxide, titanium dioxide, vanadium dioxide, chromium dioxide, manganese dioxide, tungsten dioxide, ruthenium dioxide, osmium dioxide, and iridium dioxide.
The host compounds of two-dimensional structure include titanium disulfide, zirconium disulfide, hafnium disulfide, vanadium disulfide, niobium disulfide, tantalum disulfide, chromium disulfide, molybdenum disulfide, tungsten disulfide, rhenium disulfide, platinum disulfide, tin disulfide, lead disulfide, titanium diselenide, zirconium diselenide, hafnium diselenide, vanadium diselenide, niobium diselenide, tantalum diselenide, chromium diselenide, molybdenum diselenide, tungsten diselenide, rhenium diselenide, platinum diselenide, tin diselenide, lead diselenide, titanium ditelluride, zirconium ditelluride, hafnium ditelluride, vanadium ditelluride, niobium ditelluride, tantalum ditelluride, chromium ditelluride, molybdenum ditelluride, tungsten ditelluride, rhenium ditelluride, platinum ditelluride, tin ditelluride, lead ditelluride, magnesium phosphorus trisulfide, calcium phosphorus trisulfide, vanadium phosphorus trisulfide, manganese phosphorus trisulfide, iron phosphorus trisulfide, cobalt phosphorus trisulfide, nickel phosphorus trisulfide, palladium phosphorus trisulfide, zinc phosphorus trisulfide, cadmium phosphorus trisulfide, mercury phosphorus trisulfide, tin phosphorus trisulfide, magnesium phosphorus triselenide, calcium phosphorus triselenide, vanadium phosphorus triselenide, manganese phosphorus triselenide, iron phosphorus triselenide, cobalt phosphorus triselenide, nickel phosphorus triselenide, palladium phosphorus triselenide, zinc phosphorus triselenide, cadmium phosphorus triselenide, mercury phosphorus triselenide, tin phosphorus triselenide, chromium phosphorus tetrasulfide, tantalum sulfide carbide, molybdenum trioxide, octadecamolybdenum dopentacontaoxide (18-molubdenum 52-oxide), divanadium pentaoxide gel, iron oxychloride, titanium oxychloride, vanadium oxychloride, chromium oxychloride, aluminum oxychloride, bismuth oxychloride, xcex1-zirconium nitride chloride, xcex2-zirconium nitride chloride, xcex1-zirconium nitride bromide, xcex2-zirconium nitride bromide, zirconium nitride iodide, titanium nitride chloride, titanium nitride bromide, titanium nitride iodide, graphite, and polyacene.
The host compounds of one-dimensional structure include titanium trisulfide, niobium triselenide, potassium iron disulfide, polyacetylene, polyaniline, polypyrrole, polythiophene, poly(p-phenylene), poly(triphenylene), polyazulene, polyfluorene, polynaphthalene, polyanthracene, polyfuran, polycarbazole, tetrathiafluvalene-substituted polystyrene, ferrocene-substituted polyethylene, carbazole-substituted polyethylene, and polyoxyphenazine.
The host compounds of a molecular solid include tetracyanoquinodimethane, and tetrathiafluvalene.
The host compound [Q] may be a mixture of two or more of the above host compounds.
The number of reduction, k, is preferably in the range of 0 less than kxe2x89xa63, more preferably 0 less than kxe2x89xa62 for high catalytic activity for olefin polymerization, but is not especially limited thereto.
The Lewis base or a cyclopentadienyl group, L2, may be one capable of coordinating with En+. The Lewis base includes water, amine compounds, nitrogen-containing heterocyclic compounds; ethers such as ethyl ether and n-butyl ether; amides such as formamide, N-methylformamide, N,N-dimethylformamide, and N-methylacetamide; alcohols such as methyl alcohol, and ethyl alcohol; diols such as 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol; glycerin, polyethylene glycol, diglyme, 1,2-dimethoxyethane, trimethyl phosphate, hexamethylphosphoramide, tri-n-butylphosphine oxide, 1,4-dioxane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, and propylene carbonate. The Lewis base, L2, may be a mixture of two or more of the above compounds.
The number of the Lewis base, h, is preferably in the range of 0xe2x89xa6hxe2x89xa610.
The n-valent guest cation, En+, may be a cation containing at least one atom selected from the group of atoms of Groups 1 to 14 of Periodic Table. The valency, n, of the guest cation is in the range of 0 less than nxe2x89xa610. For higher catalytic activity for olefin polymerization, the En+ is at least one cation selected from the group of cations represented by General Formulas (37), (38), (39), and (40):
R212R22NH+xe2x80x83xe2x80x83(37)
where R212R22N is an amine: R21 being independently a hydrogen atom, or an aliphatic hydrocarbon group of 1 to 30 carbons, R22 being independently a hydrogen atom, an aliphatic hydrocarbon group of 1 to 30 carbons, or an aromatic hydrocarbon group of 1 to 50 carbons,
T1H+xe2x80x83xe2x80x83(38)
where T1 is a nitrogen-containing heterocyclic compound,
(R23)+xe2x80x83xe2x80x83(39)
where (R23)+ is a carbonium cation of 1 to 50 carbons, or a tropylium cation, and
Gn+xe2x80x83xe2x80x83(40)
where G is an atom selected form atoms of Groups 1 to 14 of Periodic Table , and Gn+ is an n-valent cation.
The amine, R212R22N, includes aliphatic amines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, t-butylamine, allylamine, cyclopentylamine, dimethylamine, diethylamine, diallylamine, trimethylamine, tri-n-butylamine, triallylamine, hexylamine, 2-aminoheptane, 3-aminoheptane, n-heptylamine, 1,5-dimethylhexylamine, 1-methylheptylamine, n-octylamine, t-octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, cyclohexylamine, cycloheptylamine, cyclohexylmethylamine, 2-methylcyclohexylamine, 4-methylcyclohexylamine, 2,3-dimethylcyclohexylamine, cyclododecylamine, 2-(1-cyclohexenyl)ethylamine, geranylamine, N-methylhexylamine, dihexylamine, bis(2-ethylhexyl)amine, dioctylamine, didecylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-isopropylcyclohexylamine, N-t-butylcyclohexylamine, N-allylcyclohexylamine, N,N-dimethyloctylamine, N,N-dimethylundecylamine, N,N-dimethyldodecylamine, N,N-dimethyloctadecylamine, N,N-dioctadecylmethylamine, N,N-dioleylmethylamine, trihexylamine, triisooctylamine, trioctylamine, triisodecylamine, tridodecylamine, N,N-dimethylcyclohexylamine, and N,N-diethylcyclohexylamine; and aromatic amines such as aniline, N-methylaniline, N-ethylaniline, N-allylaniline, o-toluidine, m-toluidine, p-toluidine, N,N-dimethylaniline, N-methyl-o-toluidine, N-methyl-m-toluidine, N-methyl-p-toluidine, N-ethyl-o-toluidine, N-ethyl-m-toluidine, N-ethyl-p-toluidine, N-allyl-o-toluidine, N-allyl-m-toluidine, N-allyl-p-toluidine, N-propyl-o-toluidine, N-propyl-m-toluidine, N-propyl-p-toluidine, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, N,N-diethylaniline, 2-isopropylaniline, 4-isopropylaniline, 2-t-butylaniline, 4-n-butylaniline, 4-s-butylaniline, 4-t-butylaniline, 2,6-diethylaniline, 2-isopropyl-6-methylaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p,-phenetidine, 1-aminonaphthalene, 2-aminonaphthalene, 1-aminofluorene, 2-aminofluorene, 3-aminofluorene, 4-aminofluorene, 5-aminoindene, 2-aminobiphenyl, 4-aminobiphenyl, N,2,3-trimethylaniline, N,2,4-trimethylaniline, N,2,5-trimethylaniline, N,2,6-trimethylaniline, N,3,4-trimethylaniline, N,3,5-trimethylaniline, N-methyl-2-ethylaniline, N-methyl-3-ethylaniline, N-methyl-4-ethylaniline, N-methyl-6-ethyl-o-toluidine, N-methyl-2-isopropylaniline, N-methyl-4-isopropylaniline, N-methyl-2-t-butylaniline, N-methyl-4-n-butylaniline, N-methyl-4-s-butylaniline, N-methyl-4-t-butylaniline, N-methyl-2,6-diethylaniline, N-methyl-2-isopropyl-6-methylaniline, N-methyl-p-anisidine, N-ethyl-2,3-anisidine, N,N-dimethyl-o-toluidine, N,N-dimethyl-m-toluidine, N,N-dimethyl-p-toluidine, N,N,2,3-tetramethylaniline, N,N,2,4-tetramethylaniline, N,N,2,5-tetramethylaniline, N,N,2,6-tetramethylaniline, N,N,3,4-tetramethylaniline, N,N,3,5-tetramethylaniline, N,N-dimethyl-2-ethylaniline, N,N-dimethyl-3-ethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-6-ethyl-o-toluidine, N,N-dimethyl-2-isopropylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-2-t-butylaniline, N,N-dimethyl-4-n-butylaniline, N,N-dimethyl-4-s-butylaniline, N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-2,6-diethylaniline, N,N-dimethyl-2-isopropyl-6-methylaniline, N,N-dimethyl-2-chloroaniline, N,N-dimethyl-3-chloroaniline, N,N-dimethyl-4-chloroaniline, N,N-dimethyl-2-bromoaniline, N,N-dimethyl-3-bromoaniline, N,N-dimethyl-4-bromoaniline, N,N-dimethyl-o-anisidine, N,N-dimethyl-m-anisidine, N,N-dimethyl-p-anisidine, N,N-dimethyl-o-phenetidine, N,N-dimethyl-m-phenetidine, N,N-dimethyl-p-phenetidine, N,N-dimethyl-1-aminonaphthalene, N,N-dimethyl-2-aminonaphthalene, N,N-dimethyl-1-aminofluorene, N,N-dimethyl-2-aminofluorene, N,N-dimethyl-3-aminofluorene, N,N-dimethyl-4-aminofluorene, N,N-dimethyl-5-aminoindene, N,N-dimethyl-2-aminobiphenyl, N,N-dimethyl-4-aminobiphenyl, and N,N-dimethyl-p-trimethylsilylaniline.
The nitrogen-containing heterocyclic compound, T1, includes pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, furazan, pyridine, pyridazine, pyrimidine, pyrazine, pyrroline, pyrrolidine, imidazoline, imidazolidine, pyrazoline, pyrazolidine, piperidine, piperazine, morpholine, picoline, collidine, indole, isoindole, indazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, phthalazine, purine, pteridine, carbazole, phenanthridine, acridine, phenazine, phenanthroline, indoline, isoindoline, 2,5-dimethylpyrrolidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 2,6-dimethylpiperidine, 3,3-dimethylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, 2,2,6,6-tetremethylpiperidine, 1-methylpyrrolidine, 1-methylpiperidine, 1-ethylpiperidine, 1-butylpyrrolidine, and 1,2,2,6,6-pentamethylpiperidine.
The cation represented by General Formula (39) includes triphenylmethyl cation, and tropylium cation.
The cation represented by General Formula (40) includes cations of atoms of hydrogen, lithium, sodium, potassium, rubidium, cesium, berylium, magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, niobium, tantalum, chromium, iron, nickel, copper, silver, zinc, aluminum, and tin.
The method of preparation of Component [B] is not especially limited. The examples of the method are shown below.
(a) A host compound is immersed into a solution of guest cation-forming atoms in liquid ammonia (41):                                                         (                              k                /                n                            )                        ⁢            G                    +                      [            Q            ]                          ⁢                  →                      NH            3                          ⁢                  "AutoLeftMatch"                                    [                              xe2x80x83                            ⁢                                                                    (                                          k                      /                      n                                        )                                    ⁢                                      G                                          n                      +                                                                      +                                                      ke                    -                                    ⁡                                      (                                          NH                      3                                        )                                                  +                                  [                  Q                  ]                                            ]                        →                                                                                                      G                                              (                                                  k                          /                          n                                                )                                                                    n                        +                                                              ⁡                                          (                                              NH                        3                                            )                                                        h                                ⁡                                  [                  Q                  ]                                                            k                -                                                                        (        41        )            
(b) A host compound is allowed to react with guest cation-forming atoms at a temperature from 100 to 1500xc2x0 C. (42):                                                         (                              k                /                n                            )                        ⁢            G                    +                      [            Q            ]                          ⁢                  →                                    xe2x80x83                        ⁢            Δ            ⁢                          xe2x80x83                                      ⁢                              [                                                            (                                      k                    /                    n                                    )                                ⁢                                  G                                      n                    +                                                              +                                                ke                  -                                ⁡                                  [                  Q                  ]                                                      ]                    →                                                    G                                  (                                      k                    /                    n                                    )                                                  n                  +                                            ⁡                              [                Q                ]                                                    k              -                                                          (        42        )            
(c) A host compound is allowed to react with a halide of guest cations at a temperature from 100 to 1500xc2x0 C. (43):                                           (                          k              /              n                        )                    ⁢                                                                      G                                      n                    +                                                  ⁡                                  [                                                            (                                              X                        2                                            )                                        -                                    ]                                            n                        ⁡                          [              Q              ]                                      ⁢                              →            Δ                                              -                              (                                  k                  /                  2                                )                                      ⁢                                          (                                  X                  4                                )                            2                                      ⁢                                                                              [                                                                                    (                                                  k                          /                          n                                                )                                            ⁢                                              G                                                  n                          +                                                                                      +                                          ke                      -                                        +                                          [                      Q                      ]                                                        ]                                →                                                                            G                                              (                                                  k                          /                          n                                                )                                                                    n                        +                                                              ⁡                                          [                      Q                      ]                                                                            k                    -                                                                                                          (        43        )            
xe2x80x83where X4 is a halogen atom.
(d) A host compound is immersed into a nonaqueous solution of a reducing agent (44):                               [          Q          ]                ⁢                              →                          Red              1                                            Solv            1                          ⁢                              [                                                            (                                      k                    /                    n                                    )                                ⁢                                  G                                      n                    +                                                              +                              ke                -                            +                              [                Q                ]                            +                              h                ⁡                                  (                                      Solv                    1                                    )                                                      ]                    →                                                                                          G                                          (                                              k                        /                        n                                            )                                                              n                      +                                                        ⁡                                      (                                          Solv                      1                                        )                                                  h                            ⁡                              [                Q                ]                                                    k              -                                                          (        44        )            
xe2x80x83where Red1 is a reducing reagent containing Gn+, and Solv1 is a nonaqueous solvent.
(e) A host compound is immersed into an aqueous solution of a reducing reagent (45):                               [          Q          ]                ⁢                              →                          Red              1                                                          H              2                        ⁢                          O              1                                      ⁢                              [                                                            (                                      k                    /                    n                                    )                                ⁢                                  G                                      n                    +                                                              +                              ke                -                            +                              [                Q                ]                            +                              h                ⁡                                  (                                                            H                      2                                        ⁢                    O                                    )                                                      ]                    →                                                                                          G                                          (                                              k                        /                        n                                            )                                                              n                      +                                                        ⁡                                      (                                                                  H                        2                                            ⁢                      O                                        )                                                  h                            ⁡                              [                Q                ]                                                    k              -                                                          (        45        )            
xe2x80x83where Red2 is a reducing reagent containing Gn+,
(f) A host compound as a cathode is electrochemically reduced in an electrolyte solution containing guest cations (46):                                                         (                              k                /                n                            )                        ⁢                          E                              n                +                                              +                      ke            -                    +                      [            Q            ]                    +                      h            ⁡                          (                              Solv                2                            )                                      ⁢                  →                      Solv            2                          ⁢                                                                              E                                      (                                          k                      /                      n                                        )                                                        n                    +                                                  ⁡                                  (                                      Solv                    2                                    )                                            h                        ⁡                          [              Q              ]                                            k            -                                              (        46        )            
xe2x80x83where Solv2 is water or a nonaqueous solvent,
(g) A host compound as a cathode is electrochemically reduced with an anode containing guest cations, (46),
(h) A host compound as a cathode is electrochemically reduced with an anode containing guest cation-giving atoms, (47):                                                         (                              k                /                n                            )                        ⁢            G                    +                      [            Q            ]                          ⁢                  →                      Solv            2                          ⁢                  "AutoLeftMatch"                                    [                              xe2x80x83                            ⁢                                                                    (                                          k                      /                      n                                        )                                    ⁢                                      G                                          n                      +                                                                      +                                  ke                  -                                +                                  [                  Q                  ]                                +                                  h                  ⁡                                      (                                          Solv                      2                                        )                                                              ]                        →                                                                                                      G                                              (                                                  k                          /                          n                                                )                                                                    n                        +                                                              ⁡                                          (                                              Solv                        2                                            )                                                        h                                ⁡                                  [                  Q                  ]                                                            k                -                                                                        (        47        )            
(i) A host compound is allowed to react with an amine at a temperature from 100 to 1500xc2x0 C., (48):                               [          Q          ]                ⁢                              →            Δ                                T            2                          ⁢                              [                                                            k                  ⁡                                      (                                          T                      2                                        )                                                  ⁢                                  H                  +                                            +                              ke                -                            +                              [                Q                ]                            +                              hT                2                                      ]                    →                                                    [                                                      T                    2                                    ⁢                                      H                    +                                                  ]                            k                        ⁢                                                                                (                                          T                      2                                        )                                    h                                ⁡                                  [                  Q                  ]                                                            k                -                                                                        (        48        )            
xe2x80x83where T2 is an amine,
(j) A host compound is allowed to react with a nitrogen-containing heterocyclic compound at a temperature from 100 to 1500xc2x0 C., (49):                               [          Q          ]                ⁢                              →            Δ                                T            1                          ⁢                              [                                                            k                  ⁡                                      (                                          T                      1                                        )                                                  ⁢                                  H                  +                                            +                              ke                -                            +                              [                Q                ]                            +                              hT                1                                      ]                    →                                                    [                                                      T                    1                                    ⁢                                      H                    +                                                  ]                            k                        ⁢                                                                                (                                          T                      1                                        )                                    h                                ⁡                                  [                  Q                  ]                                                            k                -                                                                        (        49        )            
The nonaqueous solvent used in Methods (d), (f), (g), and (h) includes aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as ethyl ether, and n-butyl ether; halogenated hydrocarbons such as methylene chloride, and chloroform; amides such as formamide, N-methylformamide, N,N-dimethylformamide, and N-methylacetamide; alcohols such as methyl alcohol, and ethyl alcohol; diols such as 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol; glycerin, polyethylene glycol, diglyme, 1,2-dimethoxyethane, trimethyl phosphate, hexamethylphosphoramide, tri-n-butylphosphine oxide, 1,4-dioxane, acetonitrile, tetrahydrofuran, dimethylsulfoxide, and propylene carbonate.
In Method (c), the halide of the guest cation includes lithium chloride, sodium chloride, potassium chloride, rubidium chloride, and cesium chloride.
In Method (d), the reducing reagent includes n-butyllithium, naphthalenelithium, bezophenonelithium, benzophenonesodium, and lithium iodide. The reducing agent is used at a concentration ranging from 0.001 to 10 mol/L, in an amount ranging from 0.001 to 10 mol per mol of the host compound. The reaction temperature ranges from xe2x88x92100 to 100xc2x0 C., but is not limited thereto. The reaction time ranges from one minute to 60 days, but is not limited thereto.
In Method (e), the reducing reagent includes sodium dithionite, sodium boron hydride, and sodium sulfide. The reducing reagent is used at a concentration ranging from 0.001 to 10 mol/L, in an amount ranging from 0.001 to 10 mol per mol of the host compound. The reaction temperature ranges from 0 to 100xc2x0 C., but is not limited thereto. The reaction time ranges from one minute to 60 days, but is not limited thereto.
In Method (f), the electrolyte includes salts of the guest cation: chloride, phosphate, sulfate, nitrate, carbonate, perchlorate, formate, acetate, propionate, oxalate, malonate, succinate, citrate, tetrafluoroborate, and hexafluorophosphate. The electrolyte may be used at a concentration ranging from 0.001 to 10 mol/L.
In Method (g), the anode material is not specially limited, and is exemplified by alkali metal salts of graphite.
In Method (h), the anode material is not specially limited, and is exemplified by lithium.
In Method (i), the amine compound is exemplified by ammonia, and the amines represented by R212R22N.
Component [B] may be treated before use with a salt, an acid, and/or a Lewis base.
The salt for the salt treatment is a compound constituted of a cation containing at least one atom selected from atoms of Groups 1 to 14 of Periodic Table, and at least one anion selected from halogen anions, inorganic acid anions, and organic acid anions. The cation constituting the salt is preferably at least one cation selected from the group of cations represented by General Formulas (37), (38), (39), and (40). The anion constituting the salt is preferably at least one anion selected from the group of anions of fluorine, chlorine, bromine, iodine, phosphate, sulfate, nitrate, carbonate, perchlorate, formate, acetate, propionate, oxalate, malonate, succinate, citrate, acetylacetonate, tetrafluoroborate, and hexafluorophosphate.
The salt constituted of a cation represented by General Formula (37) and a chloride anion is exemplified by hydrochlorides of the amines represented by the aforementioned formula, R212R22N.
The salt constituted of a cation represented by General Formula (38) and a chloride anion is exemplified by hydrochlorides of the nitrogen-containing heterocyclic compounds represented by the aforementioned formula, T1.
The salt constituted of a cation represented by General Formula (39) and a halogen anion is exemplified by triphenylmethyl chloride, and tropylium bromide.
The salt containing the cation represented by General Formula (40) includes lithium chloride, sodium chloride, sodium phosphate, sodium sulfate, sodium nitrate, sodium formate, sodium acetete, sodium oxalate, sodium citrate, potassium chloride, rubidium chloride, cesium chloride, beryllium chloride, magnesium chloride, magnesium phosphate, magnesium sulfate, magnesium nitrate, magnesium perchlorate, magnesium acetate, magnesium oxalate, magnesium succinate, calcium chloride, strontium chloride, barium chloride, titanium chloride, zirconium chloride, hafnium chloride, niobium chloride, tantalum chloride, chromium chloride, iron chloride, nickel chloride, copper chloride, silver chloride, silver bromide, zinc chloride, aluminum chloride, aluminum phosphate, aluminum sulfate, aluminum nitrate, aluminum oxalate, tin chloride, and ferrocenium sulfate.
The acid used for the acid treatment includes hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, carbonic acid, perchloric acid, formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, and citric acid, and mixtures of two or more thereof.
The Lewis base used for the Lewis base treatment includes water, ammonia, the aforementioned amines represented by R212R22N; the aforementioned nitrogen-containing heterocyclic compound represented by T1; ethers such as ethyl ether, and n-butyl ether; amides such as formamide, N-methylformamide, N,N-dimethylformamide, and N-methylacetamide; alcohols such as methyl alcohol, and ethyl alcohol; diols such as 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol; glycerin, polyethylene glycol, diglyme, 1,2-dimethoxyethane, trimethyl phosphate, hexamethylphosphoramide, tri-n-butylphosphine oxide, 1,4-dioxane, acetonitrile, tetrahydrofuran, dimethylsulfoxide, and propylene carbonate; and mixtures of two or more thereof.
The salt treatment, acid treatment, and/or Lewis base treatment can be conducted, for example, by immersing at least one reduction product selected from the products of reduction reaction of Methods (a) to (j) into a salt, an acid, and/or a Lewis base, or a solution of a salt, an acid, and/or a Lewis base.
In the case where the salt treatment, the acid treatment, and/or the Lewis base treatment are combined, the treatments may be conducted in various manners: successive treatment with a salt and an acid, with a salt and a Lewis base, with an acid and a salt, with an acid and a Lewis base, with a Lewis base and a salt, or with Lewis base and an acid; simultaneous treatment with a salt and an acid, with a salt and a Lewis acid, or with an acid and a Lewis base; salt treatment and following simultaneous treatment with an acid and a Lewis base, acid treatment and following simultaneous treatment with salt and a Lewis base, Lewis base treatment and following simultaneous treatment with a salt and an acid; simultaneous treatment with a salt and an acid and following Lewis base treatment, simultaneous treatment with a salt and a Lewis base and following acid treatment, simultaneous treatment with an acid and a Lewis base and following salt treatment; or simultaneous treatment with a salt, an acid, and a Lewis base.
The conditions for the treatment with a salt, an acid, or a Lewis base are not specially limited. Preferably, the salt, the acid, or the Lewis base is used at a concentration ranging from 0.001 to 10 mol/L, at a ratio of 0.001 to 10 moles per mole of the guest cation in the reduction product. The treatment temperature ranges preferably from xe2x88x92100 to 150xc2x0 C. Treatment time ranges preferably from one minute to 60 days.
The solvent for the treatment with a salt, an acid, or a Lewis base includes aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; alcohols such as methyl alcohol, and ethyl alcohol; ethers such as ethyl ether, and n-butyl ether; halogenated hydrocarbons such as methylene chloride, and chloroform; 1,4-dioxane, acetonitrile, tetrahydrofuran, dimethylsulfoxide, propylene carbonate, water, and aqueous ammonia; and mixtures of two or more of the above. solvents.
Component [A] in the present invention includes metallocenes containing a transition metal atom such as scandium, yttrium, lanthanum, samarium, titanium, zirconium, hafnium, vanadium, niobium, chromium, and molybdenum. Of these, a metallocene compound is preferred which contains titanium, zirconium, or hafnium.
Specifically, Component [A] is a metallocene represented by General Formula (1): 
where M1 is an atom of titanium, zirconium, or hafnium; each X1 is independently a hydrogen atom, a halogen atom, or a hydrocarbon group of 1 to 20 carbons; and R1, which is a ligand of M1, represented by General Formula (2), (3), (4), or (5): 
(wherein each R2 is independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbons, an amino group-containing hydrocarbon group of 1 to 20 carbons, or oxygen-containing hydrocarbon group of 1 to 20 carbons); or a metallocene represented by General Formula (6) or (7): 
where M2 is an atom of titanium, zirconium, or hafnium; each X2 is independently a hydrogen atom, a halogen atom, or a hydrocarbon group of 1 to 20 carbons; and R3 and R4 are independently a ligand of M2 and represented by General Formula (8), (9), (10), or (11): 
(wherein each R8 is independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbons, an amino group-containing hydrocarbon group of 1 to 20 carbons, or oxygen-containing hydrocarbon group of 1 to 20 carbons), the ligands forming a sandwich structure together with M2; R5 and R6 are independently a ligand of M2 and represented by General Formula (12), (13), (14), or (15): 
(wherein each R9 is independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbons, an amino group-containing hydrocarbon group of 1 to 20 carbons, or oxygen-containing hydrocarbon group of 1 to 20 carbons), the ligands forming a sandwich structure together with M2; R7 is represented by General Formula (16) or (17): 
(wherein each R10 is independently a hydrogen atom, or a hydrocarbon group of 1 to 20 carbons; M3 is an atom of silicon, germanium, or tin), R7 forming a bridge between R5 and R6, and p is an integer from 1 to 5; or a metallocene represented by General Formula (18), (19), (20), or (21): 
where M4 is an atom of titanium, zirconium, or hafnium; each of X3 is independently a hydrogen atom, a halogen atom, or a hydrocarbon group of 1 to 20 carbons; L1 is a Lewis base, w is a number in the range of 0xe2x89xa6wxe2x89xa63; JR11qxe2x88x921 and JR11q2 are independently a heteroatom ligand of M4; J is an element of Group 15 of Periodic Table of coordination number 3 or an element of Group 16 of Periodic Table of coordination number 2; each R11 is independently a hydrogen atom, a halogen atom, or a hydrocarbon group of 1 to 20 carbons; q is a coordination number of the element J; R12 is a ligand of M and represented by General Formula (22), (23), (24), or (25): 
(wherein each R15 is independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbons, an amino group-containing hydrocarbon group of 1 to 20 carbons, or oxygen-containing hydrocarbon group of 1 to 20 carbons), each R14 is independently a ligand of M4 and represented by General Formula (26), (27), (28), or (29): 
(wherein each of R16 is independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbons, an amino group-containing hydrocarbon group of 1 to 20 carbons, or oxygen-containing hydrocarbon group of 1 to 20 carbons); R13 is represented by General Formula (30) or (31): 
(wherein each R17 is independently a hydrogen atom, or a hydrocarbon group of 1 to 20 carbons; M5 is an atom of silicon, germanium, or tin), R13 forming a bridge between R14 and JR11qxe2x88x922; and r is an integer of 1 to 5. Two of more of the metallocenes can be used combinedly.
The metallocene represented by General Formula (1) includes trichlorides of zirconium such as
(cyclopentadienyl)zirconium trichloride,
(methylcyclopentadienyl)zirconium trichloride,
(1,2-dimethylcyclopentadienyl)zirconium trichloride,
(1,3-dimethylcyclopentadienyl)zirconium trichloride,
(1,2,3-trimethylcyclopentadienyl)zirconium trichloride,
(1,2,4-trimethylcyclopentadienyl)zirconium trichloride,
(tetramethycyclopentadienyl)zirconium trichloride,
(pentamethylcyclopentadienyl)zirconium trichloride,
(n-propylcyclopentadienyl)zirconium trichloride,
(1,2-di-n-propylcyclopentadienyl)zirconium trichloride,
(1,3-di-n-propylcyclopentadienyl)zirconium trichloride,
(isopropylcyclopentadienyl)zirconium trichloride,
(n-butylcyclopentadienyl)zirconium trichloride,
(1,2-di-n-butylcyclopentadienyl)zirconium trichloride,
(1,3-di-n-butylcyclopentadienyl)zirconium trichloride,
(isobutylcyclopentadienyl)zirconium trichloride,
(t-butylcyclopentadienyl)zirconium trichloride,
(indenyl)zirconium trichloride,
(tetrahydroindenyl)zirconium trichloride,
(fluorenyl)zirconium trichloride, and
(octahydrofluorenyl)zirconium trichloride; and trimethyl derivatives, triethyl derivatives, trihydro derivatives, triphenyl derivatives, and tribenzyl derivatives of the above zirconium compounds. Further, compounds derived by replacing the zirconium atom of the above zirconium compound by a titanium atom or a hafnium atom are also useful therefor. The above compounds may be used in combination of two or more thereof.
The metallocene represented by General Formula (6) or (7) includes dichlorides of zirconium such as
bis(cyclopentadienyl)zirconium dichloride,
bis(methylcyclopentadienyl)zirconium dichloride,
bis(1,2-dimethylcyclopentadienyl)zirconium dichloride,
bis(1,3-dimethylcyclopentadienyl)zirconium dichloride,
bis(1,2,3-trimethylcyclopentadienyl)zirconium dichloride,
bis(1,2,4-trimethylcyclopentadienyl)zirconium dichloride,
bis(tetramethycyclopentadienyl)zirconium dichloride,
bis(pentamethylcyclopentadienyl)zirconium dichloride,
bis(n-propylcyclopentadienyl)zirconium dichloride,
bis (1,2-di-n-propylcyclopentadienyl)zirconium dichloride,
bis(1,3-di-n-propylcyclopentadienyl)zirconium dichloride,
bis(isopropylcyclopentadienyl)zirconium dichloride,
bis(n-butylcyclopentadienyl)zirconium dichloride,
bis(1,2-di-n-butylcyclopentadienyl)zirconium dichloride,
bis(1,3-di-n-butylcyclopentadienyl)zirconium dichloride,
bis(isobutylcyclopentadienyl)zirconium dichloride,
bis(t-butylcyclopentadienyl)zirconium dichloride,
bis(indenyl)zirconium dichloride,
bis(tetrahydroindehyl)zirconium dichloride,
bis(fluorenyl)zirconium dichloride,
bis(octahydrofluorenyl)zirconium dichloride,
(cyclopentadienyl)(indenyl)zirconium dichloride,
(cyclopentadienyl)(fluorenyl)zirconium dichloride,
(fluorenyl)(indenyl)zirconium dichloride,
methylenebis(cyclopentadienyl)zirconium dichloride,
methylenebis(2-methylcyclopentadienyl)zirconium dichloride,
methylenebis(3-methylcyclopentadienyl)zirconium dichloride,
methylenebis(2,3-dimethylcyclopentadienyl)zirconium dichloride,
methylenebis(2,4-dimethylcyclopentadienyl)zirconium dichloride,
methylenebis(2,5-dimethylcyclopentadienyl)zirconium dichloride,
methylenebis(3,4-dimethylcyclopentadienyl)zirconium dichloride,
methylenebis(tetramethylcyclopentadienyl)zirconium dichloride,
methylenebis(2-n-butylcyclopentadienyl)zirconium dichloride,
methylenebis(3-n-butylcyclopentadienyl)zirconium dichloride,
methylenebis(2-t-butylcyclopentadienyl)zirconium dichloride,
methylenebis(3-t-butylcyclopentadienyl)zirconium dichloride,
methylenebis(indenyl)zirconium dichloride,
methylenebis(tetrahydroindenyl)zirconium dichloride,
methylenebis(2-methyl-1-indenyl)zirconium dichloride,
methylenebis(fluorenyl)zirconium dichloride,
methylenebis(octahydrofluorenyl)zirconium dichloride,
methylene(cyclopentadienyl)(indenyl)zirconium dichloride,
methylene(cyclopentadienyl)(tetrahydroindenyl)zirconium dichloride,
methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
methylene(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,
methylene(fluorenyl)(indenyl)zirconium dichloride,
ethylenebis(indenyl)zirconium dichloride,
ethylenebis(tetrahydroindenyl)zirconium dichloride,
ethylenebis(2-methyl-1-indenyl)zirconium dichloride,
ethylenebis(2-ethyl-1-indenyl)zirconium dichloride,
ethylenebis(2,4-dimethyl-1-indenyl)zirconium dichloride,
ethylenebis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
ethylenebis(2-methyl-4-naphthyl-1-indenyl)zirconium dichloride,
ethylenebis(2-methyl-4,6-diisopropyl-1-indenyl)zirconium dichloride,
isopropylidenebis(cyclopentadienyl)zirconium dichloride,
isopropylidenebis(2-methylcyclopentadienyl)zirconium dichloride,
isopropylidenebis(3-methylcyclopentadienyl)zirconium dichloride,
isopropylidenebis(2,3-dimethylcyclopentadienyl)zirconium dichloride,
isopropylidenebis(2,4-dimethylcyclopentadienyl)zirconium dichloride,
isopropylidenebis(2,5-dimethylcyclopentadienyl)zirconium dichloride,
isopropylidenebis(3,4-dimethylcyclopentadienyl)zirconium dichloride,
isopropylidenebis(tetramethylcyclopentadienyl)zirconium dichloride,
isopropylidenebis(2-n-butylcyclopentadienyl)zirconium dichloride,
isopropylidenebis(3-n-butylcyclopentadienyl)zirconium dichloride,
isopropylidenebis(2-t-butylcyclopentadienyl)zirconium dichloride,
isopropylidenebis(3-t-butylcyclopentadienyl)zirconium dichloride,
isopropylidenebis(indenyl)zirconium dichloride,
isopropylidenebis(tetrahydroindenyl)zirconium dichloride,
isopropylidenebis(2-methyl-1-indenyl)zirconium dichloride,
isopropylidenebis (fluorenyl)zirconium dichloride,
isopropylidenebis(octahydrofluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(indenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(tetrahydroindenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(fluorenyl) zirconium dichloride,
isopropylidene(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(2,7-dimethylfluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(2-dimethylaminofluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(2-diisopropylaminofluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(4-dimethylaminofluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(4-diisopropylaminofluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)[2,7-bis(dimethylamino)fluorenyl]zirconium dichloride,
isopropylidene(cyclopentadienyl)[2,7-bis(diisopropylamino)fluorenyl]zirconium dichloride,
isopropylidene(cyclopentadienyl)(2-methoxyfluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(4-methoxyfluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(2,7-dimethoxyfluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(2,3,7-trimethoxyfluorenyl)zirconium dichloride,
isopropylidene(fluorenyl)(indenyl)zirconium dichloride,
dimethylsilanediylbis(cyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(2-methylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(3-methylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(2,3-dimethylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(2,4-dimethylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(2,5-dimethylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(3,4-dimethylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(tetramethylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(2-n-butylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(3-n-butylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(2-t-butylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(3-t-butylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(indenyl)zirconium dichloride,
dimethylsilanediylbis(tetrahydroindenyl)zirconium dichloride,
dimethylsilanediylbis(2-methyl-1-indenyl)zirconium dichloride,
dimethylsilanediylbis(2-ethyl-1-indenyl)zirconium dichloride,
dimethylsilanediylbis(2,4-dimethyl-1-indenyl)zirconium dichloride,
dimethylsilanediylbis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
dimethylsilanediylbis(2-methyl-4-naphthyl-1-indenyl)zirconium dichloride,
dimethylsilanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)zirconium dichloride,
dimethylsilanediylbis(fluorenyl)zirconium dichloride,
dimethylsilanediylbis(octahydrofluorenyl)zirconium dichloride,
dimethylsilanediyl(cyclopentadienyl)(indenyl)zirconium dichloride,
dimethylsilanediyl(cyclopentadienyl)(tetrahydroindenyl)zirconium dichloride,
dimethylsilanediyl(cyclopentadienyl)(fluorenyl)zirconium dichloride,
dimethylsilanediyl(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,
dimethylsilanediyl(fluorenyl)(indenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(2,7-dimethylfluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(2-dimethylaminofluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(2-diisopropylaminofluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(4-dimethylaminofluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(4-diisopropylaminofluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)[2,7-bis(dimethylamino)fluorenyl]zirconium dichloride,
diphenylmethylene(cyclopentadienyl)[2,7-bis(diisopropylamino)fluorenyl]zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(2-methoxyfluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(4-methoxyfluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(2,7-dimethoxyfluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(2,3,7-trimethoxyfluorenyl)zirconium dichloride,
diphenylsilanediyl(cyclopentadienyl)(fluorenyl)zirconium dichloride,
diphenylsilanediyl(cyclopentadienyl)(2,7-dimethylfluorenyl)zirconium dichloride,
diphenylsilanediyl(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,
diphenylsilanediyl(cyclopentadienyl)(2-dimethylaminofluorenyl)zirconium dichloride,
diphenylsilanediyl(cyclopentadienyl)(2-diisopropylaminofluorenyl)zirconium dichloride,
diphenylsilanediyl(cyclopentadienyl)(4-dimethylaminofluorenyl)zirconium dichloride,
diphenylsilanediyl(cyclopentadienyl)(4-diisopropylaminofluorenyl)zirconium dichloride,
diphenylsilanediyl(cyclopentadienyl)[2,7-bis(dimethylamino)fluorenyl]zirconium dichloride,
diphenylsilanediyl(cyclopentadienyl)[2,7-bis(diisopropylamino)fluorenyl]zirconium dichloride,
diphenylsilanediyl(cyclopentadienyl)(2-methoxyfluorenyl)zirconium dichloride,
diphenylsilanediyl(cyclopentadienyl)(4-methoxyfluorenyl)zirconium dichloride,
diphenylsilanediyl(cyclopentadienyl)(2,7-dimethoxyfluorenyl)zirconium dichloride, and
diphenylsilanediyl(cyclopentadienyl)(2,3,7-trimethoxyfluorenyl)zirconium dichloride;
and dimethyl derivatives, diethyl derivatives, dihydro derivatives, diphenyl derivatives, and dibenzyl derivatives of the above zirconium compounds. Further, compounds derived by replacing the zirconium atom of the above zirconium compound by a titanium atom or a hafnium atom are also useful therefor. The above compounds may be used in combination of two or more thereof.
The metallocene represented by General Formula (18), (19), (20), or (21) includes dichlorides of zirconium such as
pentamethylcyclopentadienyl-di-t-butylphosphinozirconium dichloride,
pentamethylcyclopentadienyl-di-t-butylamidozirconium dichloride,
pentamethylcyclopentadienyl-n-butoxidozirconium dichloride,
dimethylsilanediyltetramethylcyclopentadienyl-t-butylamidozirconium dichloride,
dimethylsilanediyl-2-t-butylcyclopentadienyl-t-butylamidozirconium dichloride,
dimethylsilanediyl-3-t-butylcyclopentadienyl-t-butylamidozirconium dichloride,
dimethylsilanediyl-2-trimethylsilylcyclopentadienyl-t-butylamidozirconium dichloride,
dimethylsilanediyl-3-trimethylsilylcyclopentadienyl-t-butylamidozirconium dichloride,
dimethylsilanediyltetramethylcyclopentadienylphenylamidozirconium dichloride,
methylphenylsilanediyltetramethylcyclopentadienyl-t-butylamidozirconium dichloride,
dimethylsilanediyltetramethylcyclopentadienyl-p-n-butylphenylamidozirconium dichloride,
dimethylsilanediyltetramethylcyclopentadienyl-p-methoxyphenylamidozirconium dichloride,
dimethylsilanediyl-2-t-butylcyclopentadienyl-2,5-di-t-butylphenylamidozirconium dichloride,
dimethylsilanediyl-3-t-butylcyclopentadienyl-2,5-di-t-butylphenylamidozirconium dichloride,
dimethylsilanediylindenyl-t-butylamidozirconium dichloride,
dimethylsilanediyltetramethylcyclopentadienylcyclohexylamidozirconium dichloride,
dimethylsilanediylfluorenylcyclohexylamidozirconiumdichloride, and
dimethylsilanediyltetramethylcyclopentadienylcyclododecylamidozirconium dichloride;
and dimethyl derivativives, diethyl derivatives, dihydro derivatives, diphenyl derivatives, and dibenzyl derivatives of the above zirconium compounds. Further, compounds derived by replacing the zirconium atom of the above zirconium compound by a titanium atom or a hafnium atom are also useful therefor. The above compounds may be used in combination of two or more thereof.
Component [C] in the present invention is an organoaluminum compound preferably represented by General Formula (32):
AlR183xe2x80x83xe2x80x83(32)
where each R18 is independently a hydrogen atom or a hydrocarbon group of 1 to 20 carbons, for obtaining an olefin polymer with high catalytic activity.
The organoaluminum compound represented by General Formula (32) includes trimethylaluminum, dimethylaluminum hydride, triethylaluminum, diethylaluminum hydride, tri-n-propylaluminum, di-n-propylaluminum hydride, triisopropylaluminum, diisopropylaluminum hydride, tri-n-butylaluminum, di-n-butylaluminum hydride, triisobutylaluminum, diisobutylaluminum hydride, tri-t-butylaluminum, di-t-butylaluminum hydride, tri-n-hexylaluminum, di-n-hexylaluminum hydride, triisohexylaluminum, diisohexylaluminum hydride, tri-n-octylaluminum, di-n-octylaluminum hydride, triisooctylaluminum, and diisooctylaluminum hydride.
Component [D] in the present invention is an organoalkaline earth metal compound preferably represented by General Formula (33):
M6R192xe2x80x83xe2x80x83(33)
where each M6 is an alkaline earth metal of Group 2 of Periodic Table, and each R19 is independently a hydrocarbon group of 1 to 20 carbons; or an organozinc compound represented by General Formula (34):
ZnR202xe2x80x83xe2x80x83(34)
where each R20 is independently a hydrocarbon group of 1 to 20 carbons, for obtaining an olefin polymer with high catalytic activity.
The organoalkaline earth metal compound represented by General Formula (33) includes magnesium such as dimethylmagnesium, ethylmethylmagnesium, methyl-n-propylmagnesium, methylisopropylmagnesium, n-butylmethylmagnesium, isobutylmethylmagnesium, t-butylmethylmagnesium, methylphenylmagnesium, diethylmagnesium, ethyl-n-propylmagnesium, ethylisopropylmagnesium, n-butylethylmagnesium, isobutylethylmagnesium, t-butylethylmagnesium, ethylphenylmagnesium, di-n-propylmagnesium, n-propylisopropylmagnesium, n-butyl-n-propylmagnesium, isobutyl-n-propylmagnesium, t-butyl-n-propylmagnesium, phenyl-n-propylmagnesium, diisopropylmagnesium, n-butylisopropylmagnesium, isobutylisopropylmagnesium, t-butylisopropylmagnesium, phenylisopropylmagnesium, di-n-butylmagnesium, n-butylisobutylmagnesium, n-butyl-t-butylmagnesium, n-butylphenylmagnesium, diisobutylmagnesium, isobutyl-t-butylmagnesium, isobutylphenylmagnesium, di-t-butylmagnesium, t-butylphenylmagnesium, and diphenylmagnesium; and compounds derived by replacing the magnesium of the above magnesium compounds by beryllium, calcium, strontium, barium, or radium. Of these, the magnesium compounds are suitable, n-butylethylmagnesium being more suitable. The above compounds may be used in combination of two or more thereof.
The organozinc compound represented by General Formula (34) includes dimethylzinc, ethylmethylzinc, methyl-n-propylzinc, methylisopropylzinc, n-butylmethylzinc, isobutylmethylzinc, t-butylmethylzinc, methylphenylzinc, diethylzinc, ethyl-n-propylzinc, ethylisopropylzinc, n-butylethylzinc, isobutylethylzinc, t-butylethylzinc, ethylphenylzinc, di-n-propylzinc, n-propylisopropylzinc, n-butyl-n-propylzinc, isobutyl-n-propylzinc, t-butyl-n-propylzinc, phenyl-n-propylzinc, diisopropylzinc, n-butylisopropylzinc, isobutylisopropylzinc, t-butylisopropylzinc, phenylisopropylzinc, di-n-butylzinc, n-butylisobutylzinc, n-butyl-t-butylzinc, n-butylphenylzinc, diisobutylzinc, isobutyl-t-butylzinc, isobutylphenylzinc, di-t-butylzinc, t-butylphenylzinc, and diphenylzinc. Of these, diethylzinc is preferable. The above compounds may be used in combination of two or more thereof.
In one embodiment of the present invention, the olefin polymerization catalyst is prepared by bringing Component [A], Component [B], and Component [C] into contact. Preferably, Component [B] and a part or the entire of Component [C] is preliminarily brought together into contact to diminish the adverse effect of impurities in Component [B], but the method of the contact is not specially limited.
In another embodiment of the present invention, the olefin polymerization catalyst is prepared by bringing Component [A], Component [B], Component [C], and Component [D] into contact. Preferably, Component [A], Component [B], and a part or the entire of Component [C] are preliminarily brought together into contact, and a part or the entire of Component [D] are brought into contact therewith to obtain high catalyst activity for olefin polymerization, but the method of the contact is not specially limited.
The solvent for the contact of the catalyst components includes aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as ethyl ether, and n-butyl ether; halogenated hydrocarbons such as methylene chloride and chloroform; 1,4-dioxane, acetonitrile, and tetrahydrofuran.
The temperature of the contact ranges preferably from 0 to 200xc2x0 C.
The amounts of the catalyst components to be used are in the ranges below for higher catalyst activity and lower ash content of the produced polymer. For 1 gram of Component [B], Component [A] ranges from 0.0001 to 100 mmol, preferably from 0.001 to 10 mmol; Component [C] ranges from 0.001 to 10000 mmol, preferably from 0.01 to 1000 mmol; and Component [D], when it is used, ranges from 0.0001 to 1000 mmol, preferably from 0.001 to 100 mmol. The molar ratio of Component [A] to Component [C] ranges from 1:0.1 to 1:10000, preferably 1:1 to 1:1000. The molar ratio of Component [A] to Component [D] ranges from 1:0.1 to 1:10000, preferably from 1:1 to 1:1000.
The catalyst prepared as above may used without washing, or after washing. If necessary, Component [C] or Component [D] may be further supplemented to the prepared catalyst. The amount of the supplemented Component [C] is decided to obtain the molar ratio of Component [A] to Component [C] in the range from 1:0 to 1:10000, and the amount of the supplemented Component [D] is decided to obtain the molar ratio of Component [A] to Component [D] in the range from 1:0 to 1:10000.
The catalyst, before use for a catalyst for olefin polymer production, may be treated by preliminary polymerization of olefin such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, and styrene, and if necessary, be washed. This preliminary polymerization is preferably conducted in an inert solvent to form a polymer in an amount ranging from 0.01 to 1000 g, preferably from 0.1 to 100 g per gram of the catalyst.
An olefin polymer is produced, in the present invention, by homopolymerization of an olefin or copolymerization of olefins with the aforementioned catalyst in a solution state, a suspension state, or a gas state.
The polymerization is conducted at a polymerization temperature ranging from xe2x88x9270 to 300xc2x0 C., preferably from 0 to 250xc2x0 C., at a polymerization pressure ranging from 0.5 to 3000 kgf/cm2, preferably from 1 to 2000 kgf/cm2. Hydrogen may be introduced as a molecular weight controlling agent into the polymerization system.
The olefin polymerizable in the present invention includes xcex1-olefin such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, and vinylcycloalkane; cyclic olefins such as norbornene, and norbornadiene; dienes such as butadiene, 1,4-hexadiene; and styrene, but is not limited thereto. The olefin may be a mixture of two or more thereof.
In the polymerization in a solution state, or a suspension state, in the present invention, the polymerization solvent may be any organic solvent employed generally, specifically including halogenated hydrocarbons such as chloroform, methylene chloride, and carbon tetrachloride; aliphatic hydrocarbons of 3 to 20 carbons such as propane, n-butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; and aromatic hydrocarbons of 6 to 20 carbons such as benzene, toluene, and xylene. Otherwise, the olefin itself may be utilized as the solvent.